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Patented Jan. 19, 1932 oars 1 M TE PAT-T QFFEE MORDECAI MENDOZA, F BLACKLEY, MIANCHESTER, ENGLAND, ASSIGNOR TO IMPERIAL CHEMICAL INDUSTRIES LIMITED, OF LONDON, EN GLAND NEW PYRAZOLONES AND DYES THEREFROM 170 Drawing. Application filed July 27, 1928, Serial No. 295,851, and in Great Britain August 19, 1927.

. Renewed January 19, 1931.

In certain prior-and copending applications, Saunders Ser. No. 53,404 filed Aug. 29, 1925 (now Pat. No. 1,766,946) and Ser. No. 115,122'filed June 10, 1926 (now Pat. No.

1,766,947); Saunders & Mendoza Ser. No. 97,758 filed Mar. 26, 1926; Saunders & Mendoza Ser. No. 138,567 filed Sept. 29, 1926 (now Pat. No. 1,7 66,9418) ,and Mendoza, Ser. No. 180,618 filed April 2, 1926, there are disclosed azo and other dyes derived from intermediates of the general type wherein R and R represent aryl residues, X

represents a sulphone 80 or sulphide (S) bridge and w represents 1 or 2.

The characteristics of these compounds is that they contain a chelate group, in this case the grouping in a part of the molecule separated by the sulphone or sulphide bridge from that part or diazo compound, the diazo compound is reduced to form the hydrazine compound and the hydrazine compound is then condensed with a beta-ketonic ester to convert the hydrazine group into a pyrazolone ring.

In all the stated prior, and copending applications, the sulphone or sulphide bridge is in the para position to the hydroxy group.

In my copending applications Ser. No. 280,649 filed May 25, 1928'and Ser. No. 293,496 filed July 17, 1928 there are disclosed intermediates of the type wherein R and R represent aryl residues, X

is a sulphone or sulphide bridge and w is 1 or.2 and in which the COOH group and the X. are in ortho positions to the OH group. The intermediates disclosed in these applications Ser. No. 280,649 and 293,496 differ from those of the other acknowledged applications in that the OH group is ortho to the bridge instead of being para to the same.

The present invention relates to further developments along these lines. I have found the intermediates disclosed in Ser. Nos.

280,649 and 293,496 may be converted into new intermediates which are also useful in the manufacture of azo dyes. These new intermediates may be made from compounds having the formula wherein R represents the pyrazolone ring and the other symbols have their former designations.

I find that the following typical compounds are especially advantageous:

In the above formulae, X represents S or S R represents H, CH or C1, R represents S0 11, CQO H, CHO, N, etc. and R represents a pyrazolone ring, for example represents CH wherein R QOOH or COOC H These compounds are made from the corresponding amines (that is compounds of the type shown in formulae IIII in which there is a NH group attached to the position occupied by which are described in applications Ser. No. 2530,61 9 and 293396, and it is to be understoou that the monoamino sulphones or sulphides therein mentioned may, by my present invention be converted into pyrazolone derivatives which are valuable intermediates for azo dyes which are not appreciably changed in shade when chromed.

By coupling my new pyrazolones with diazo components, including in this term diazotized amino compounds, diazotized amino azo compounds and tetrazotized diamino compounds, I obtain new azo or polyazo dyes which dye animal fibres in a va- "riety of shades according to the nature of the diazo components selected, and are also valuable for chrome printing on cotton.

Among the advantageous compounds which may be diazotized and coupled with my new pyrazolone intermediates there may be mentioned parasubstituted anilines, such as para-nitro-aniline and sulphanilic acid. Diazotized coupling components of. the henzene and naphthalene series are advantageous, including within the term l enzene series compounds of the benzidine type.

The following generic i'orniulee can be used to represent both the intermediates and the dyes of my invention wherein R, and R represent benzene or real naphthalene residues in which the COOH and the X groups are attached to R in the ortho positions in respect to the OH group, R represents a pyrazolone residue and Y represents a substituent group selected from a class consisting of H, =NR and -N=NR -N=NR wherein R represents the coupled residue of a diazotized coupling component of the benzene or naphthalene series, R represents a divalent residue of an azo dye component of the henzene or naphthalene series and R represents the coupled residue of an azo dye component of the benzene or naphthalene series and X represents S0 or S. By the expression coupled residue of an azo dye component I mean the coupled residue from an azo dye coupling component or from a diazotized coupling component.

Another generic formula is Rs R X-I t2-N HOOC 00 wherein R represents a substituent group, such as S0 11, COOH, CHO, CV or H, R", represents CH COOH or COOC H and Z represents the structure residue of a of the henthe remainsignificance. 1s

wherein R represents a coupled diazotized coupling component Zone or naphthalene series and ing symbols have their previous Still another generic formula wherein R represents a substituent group 11c such as CH or Cl and the remaining symbols have their previous significance.

An advantageous dyestutl' falling within the purview of my invention can be represented by the formula Hooo on l rrin into neutralsolution in 200 parts of water with the aid of soda ash. To this solution 1s added 6.9 parts of sodium nitrite and the mixture is then stirred slowly into 13 parts of hydrochloric acid contained in 100 parts of water cooled to 5 C. When diazotization is complete the resulting yellow suspension is slowly added to an ice cold solution of 38 parts of sodium sulphite in parts of watei'. The deep orange solution which is so obtained is stirred for 3-4 hours during which time it is allowed to assume the laboratory temperature. A solution of 36.5 parts of hydrochloric acid in 280 part-s of water is then cautiously added, the mixture is gradually heated to boiling and kept gently boiling for a further 3 hours; stirring being maintained throughout this time. During this process the hydrazine is deposited as a thick yellow crystalline mass. While still being agitated, the mixture is then allowed to cool slowly, when it is filtered, pressed well and dried. theoretical.

ln exactly simi ar manner areproduced the corresponding hydrazines derived from 2- amino a metliyi-diphenyl sulpho-ne and 2-amino-dsulpho-Qhydroxyfi-carboXy5-chloro dipheiyl sulphone (Application Serial No. 280,- 649, 'ZHEQlQS 1 and 2). v

The same method of procedure is applicable to the amino diaryl sulphides described in Application Serial No. 293,496, Example 2, and the corresponding hydrazine compounds derived from 2amino-2'-hydroXy-4-sulph0- 3-carboXy-5-methyl dip ienyl sulphide, 5- chloro 2 hydroxy Q-amino-l-sulpho-3-carboxy diphenyl sulphide, Q-amino-l-sulphophenyl 2-hydroxy3-carboXyl-l-naphthyl sulphide etc. etc. are obtained.

Condensation of any of the above hydrazines with ethyl-acetoacetateresulting in the formation of a 3-methyl-5pyrazolone- The yield obtained is practically is carried out in manner similar to the following 43.8 parts of the hydrazine obtained as above from 2-amino-d-sulphophenyl 2-hydrony 3 carboxy l naphthyl sulphone are dissolved in 250 parts of water and 12 parts of sodium carbonate. The slightly alkaline solution so obtained is stirred and 13 parts of ethyl acetoacetate are added. The temperature of the mixture is slowly raised to 8090 1, and in the course of 5-6 hours pyrazolone formation is complete. The product is isolated as a sandy colored orystallinepowder by acidifying with strong hydrochloric acid, after cooling to laboratory temperatures. The yield is approximately 90 per cent of the theoretical.

'EccampZe 2.The hydrazinecompounds of Example 1 are convertible into the corresponding 3-carboXy-5-pyrazolone in manner similar to the following:

. 43.8 parts of the hydrazine derived from 2- amino l sulphophenyl 2 hydroxy 3 '-car- I boxy-l-naphthyl I sulphone are made into a paste with 100 parts of water and 15 parts of sodium acetate. 22.6 parts of oxalacetic ester (potassium salt) are then added and the mixture i's'agitated at 80 C. A clear solu- COOH SOBH I OH Example 3.-13.8 parts of p-nitroaniline are diazotized as usual and combined in presence of sodium carbonate with 50.4 parts of the 3-methyl-5-pyrazolone obtained as in Example 1 from 2-amino l-sulphophenyl-Q-hydroxy-S-carboxy-l-naphthyl-sulphone. Coupling results in the formation of a ellow brown dyestuif which can be isolated y the addition of common salt after giving the coupling mixture a slight mineral acidity. When dry the dyestulf is a dark orange powder soluble in water to a reddish yellow colored solution and in strong sulphuric acid to a yellowish red one from which an orange precipitate is thrown down on dilution with Water. It is very sparingly soluble in strong hydrochloric acid with formation of an orange colored solution. In strong aqueous caustic soda it gives a deep brown solution. Printed on cotton with chrome mordant, yellowish brown shades are produced of very good soap and'chlorine fastness. Dyed on wool from an acid bath similar shades are obtained which deepen slightly on after-chroming. The dyestuif has the probable formula rte-C N and after giving the solution a slight mineral acidity. The dyestuff when dried, and

ground is a bright red powder soluble in wachlorodiphenyl sulphone are used in place of ter to a red orange colored solution. \Vhen dissolved in concentrated sulphuric acid it gives a bright blue red colored solution which becomes scarlet on dilution with water. It is sparingly soluble in warm strong hydrochloric acid giving a blue red colored solution which on dilution with water changes in color to orange. It dissolves in strong aqueous caustic soda to a red brown colored solution. \Vhen printed on cotton with chrome mordant it gives red shades of very good fastness to soaping and chlorine. Wool is dyed by it from an acid bath in similar shades which are not appreciably changed on after-chroming. By combining the pyrazolone used in this and the preceding example with the diazo derivative from 17.3 parts of sulphanilic acid, the dyestuff obtained produces yellow shades on cotton and wool while the substitution of the diazo body from 22.8 parts of naphthionie acid results in the formation of a dyestulf which yields orange shades. Both of these dyestuffs show 7 good fastness to soap and chlorine. Dyestaffs of very similar shades, which are fast to soap and chlorine are also produced when the pyrazolone used in their preparation is replaced by the corresponding pyrazolone derived from Q-amino-2-hydroxyl-sulph 3-carbo:-;y-5 inethyldiphenyl sulphone and 2-amino-2 -hyd roXy-tsulpho-3-carboxyl -5- rhlorodiphenyl sulphone.

Example 5.13.8 parts of nitroaniline are diazotized as usual and combined in presence of sodium carbonate with are parts of the S-carboxy-5pyrazolone obtained from 2- amino-4l-sulphophenyl-Q-hydroxy-EB-carboxyl-naphthyl sulphone as in Example 2 above.

The dyestufl' is isolated as in Example 3.

\Vhen dyed it is a yellow red powder soluble in water to a yellow "ed solution. It dissolves in concentrated sulphuric acid to a deep red solution which gives, on diluting with water, a light red precipitate. It is only sparingly soluble in strong hydrochloric acid. It dissolves readily in strong aqueous caustic soda to an olive green colored solution. Cotton is printed by it in the presence of chrome mordant in light brown shades fast to soap and chlorine. Similar shades are produced on wool from an acid bath.

Combination of the above pyrazolone with the equivalent amount of the diazo derivative of sulphanilic acid results in the formation amino-2- hydroxy- 4-sulpho-3 carboxy- 5- the pyrazolone above mentioned.

Example 6.-The diazo compound obtained in the customary manner from 22.3 parts of naphthionic acid is combined in the presence of sodium carbonate with 43.6 parts of the 3-methyl-S-pyrazolone prepared as in Example 1 from 2-amino-Q-hydroXy-4-sulpho-3-carboxy-5-methyl diphenyl sulphide. Coupling is very rapid and, when complete, the new dyestufl is isolated as a yellowish brown powder by salting out after giving the coupling solution a slight mineral acidity. It has the probable formula COOH | OOII 0-SO3H 1130" soz i Wool is dyed by it from an acid bath in brown shades which are deepened slightly on art." Cotton is printedin the presence of chrome mordant-in light brown shades of good fastness to soaping and fairly good fastness to chlorine.

The color similarly obtained when sulphanilic acid is used as the diazo component, yields yellow shades on wool and cotton. Dyestuffs of very similar shades and fastness pyrazolone are produced when the methyl pyrazolone used above is replaced by those derived as in Example 1 from 2-amino- 2-hydroxy-d-sulpho 3 carboxy diphenyl sulphide and 2-amino4-sulphophenyl 2-hydroxy-S-carboxy-l-naphthyl sulphide.

Emmnpic '2'.-The diazo compound from 15 parts of p-amino acetanilide is coupled at about 10 C. with 48.65 parts of the 3- carboxy-S-pyrazolone prepared from 5-chloro-2-amino-2-hydroxy-el-sulpho-3 carboxy diphenyl sulphide (according to the method described in Example 2 above) dissolved in lOO parts of water and sufiicient soda ash to ensure an alkaline medium. Coupling is completed in the course of an hour.

The dyestuil' is isolated by addition of salt after making the reaction mixture neutral.

From an acid bath it dyes wool in warm brown shades to soaping. After-chroming produces no change in shade. Printed on cotton with chrome mordant red brown shades of fairly good soap and chlorine fastness are obtained.

If in place of the above car-boxy pyrazolone the corresponding compounds derived from 2- amino2-hydroXy-l-sulpho-3'-carboXy-5- methyl diphenyl sulphide and Q-aminol-sulphophenyl Q-hydroxy-3-carboXy-1-naphthyl sulphide are used as coupling components,

dyestuffs similar in shade and properties are obtained.

Ewample 8.l8.4 parts of benzidine are tetrazotized in the customary manner and the clear tetrazo solution is quickly added at 540 to a stirring solution of 137.8 parts of salicylic acid in 35 parts of sodium carbonate and 800 parts of water.

lVhen formation of the orange yellow monoazo intermediate compound is complete, a solution of 48.65 parts of the 3-carboXy-5- pyrazolone derived as in Example Zfrom 5- chloro- 2 -amino-2'-hydroxy-4L-sufpho-3-carboxy diphenyl sulphide in 400 parts of water and 12 parts of sodium carbonate is added. The second coupling proceeds with the disappearance of theorange yellow suspension of the monoazo intermediate compound and formation of a'deep red brown solution from which, on completion of the coupling, the new dyestuff is isolated as a red brown powder by salting out after giving the solution a slight mineral acidity. The dyestuff is soluble in hot water forming an orange colored solution. It givesin concentrated sulphuric acida violet colored solution from which a brown precipitate is thrown down on dilution with water. It is insoluble in strong hydrochloric acid. With strong aqueous caustic soda it gives a yellow brown colored solution. p 4

It dyes wool from an acid bath in bright orange shades fast to soaping. On afteroh'roming the shade is very slightly browned. Then printed on cotton with chrome mordant brown shades of fairly good soap and chlorine fastness are obtained.

As in Example 7, the use of the analogous carboxy pyrazolones derived from Q-aminol-sulpho-Q-hydroXy-3-carboXy-5'-m e t h y l diphenyl sulphide and Q-amino-l-sulphodiphenyl 2-hydroxy-3-oarboxy-l-naphthyl sulphide in place of the carboxy pyrazolone above mentioned results in the production of dyestuffs of very similar shades and properties.

lVhat I claim and desire to secure by Letters Patent.is:

1. In the manufacture of new dyestuf'f intermediates and new azo dyes therefrom, the steps which comprise diazotizing a diaryl compoundof the type wherein R and R represent benzene or naphthalene residues, X represents S0 or and the X and the COOH groups are attached'to R in the ortho positions in respect to the OH group; reducing the diazo compound so obtained to' the hydrazine compound and then condensing the said hydrazine compound with a beta ketonic ester.

2. In the manufacture of new dyestufi inwherein R represents a benzene or naphthalenc residue, X represents SO or S, R represents H, CH or Cl; reducing the diazo com pound so obtained to the hydrazine and then condensing the said hydrazine compound with an cthyl-aceto-acetate. i 4, In the manufacture of new dyestufi intermediates and new azo dyes therefrom, the steps which comprise diazotizing a diaryl compound of the type- Hoop 311 wherein X represents S0 or S, R represents a benzene residue, R represents H, (II-1 ,01 Cl, and R represents SO H, COOH, GHQ,

ON or H; reducing the diazo compound to the hydrazine and then condensing the said hydrazine compound ester. V v 5. In the manufacture of new dyestuffm:

with a beta-'ketonic tcrmediates and new azo dyes therefrom, the

steps which comprise diazotizing a diaryl compound of the type wherein R and R represent benzene and naphthalene residues and in which'the S02 and the COOH groups are attached to R in the ortho positions in respect to the OH group; reducing the diazo compound so obtained to the hydrazine compound and then condensing the said hydrazine compound with a beta ketonic ester.

6. In the manufacture of new dyestuif intermediates and new azo dyes therefrom, the

steps which comprise diazotizing a diaryl compound of the type H000 m wherein R represents a benzene or naphthalene residue and R represents H, CH or Cl; reducing the diazo compound so obtained to the hydrazine and then condensing the said hydrazine compound with a beta-ketonic ester.

7 In the manufacture of new dyestuif intermediates and new azo dyes therefrom, the steps which comprise diazotizing a diaryl compound of the type O-soz-nkmn wherein R represents a benzene or naphthalene residue and It represents H, CH or Cl; reducing the diazo compound so obtained to the hydrazine and then condensing the said hydrazine compound with an ethyl-aceto-acetate.

8. In the manufacture of new dyestuff intermediates and new azo dyes therefrom, the steps which comprise diazotizing a diaryl compound of the type HOOCI} (1)11 SOg-I|t2-NH2 R4 5 wherein R represents abenzene residue, R; represents H, CH or Cl, and R represents S'O H, COOH, CHO, CN or H; reducing the diazo compound to the hydrazine and then condensing the said hydrazine compound with a beta-ketonic ester.

9. In the manufacture of new dyestufl' intermediates and new azo dyes therefrom, the process which comprises diazotizing a diaryl compound of the type R1XRgl lI'I2 wherein R and R represent benzene or naphthalene residues, X represents SO or S and the X and the COOH groups are attached process which comprises diazotizing a diaryl compound of the type wherein R and R represent benzene or naphthalene residues, X represents S0 or S and the COOH groups are attached to R in the ortho positions in respect to the OH group; reducing the diazo compound so obtained to the hydrazine compound, condensing the said hydrazine compound with a beta-ketonic ester to produce a pyrazolone derivative and then coupling the so produced pyrazolone derivative with a diazotized coupling com-t ponent of the benzene or naphthalene series.

11. In the manufacture of azo dyestufi' intermediates and new azo dyes therefrom, the process which comprises diazotizing a diaryl compound of the type wherein X represents S0 or S, R represents no 0 e on I 1'15 O-X-m-Nm wherein R represents a pyrazolone ring, R, and R represent benzene or naphthalene residues, Y represents a substituent group selected from a class consisting of H,

wherein R represents the coupled residue of a diazotized coupling component of the benzene or naphthalene series, R represents a divalent residue of an azo dye component of the benzene or naphthalene series and R represents the coupled residue of an azo dye component of the benzene or naphthalene series, X repre 'sents S or S and in which the X and the COOH groups are attached to R in the ortho positions in respect to the OHgroup.

14, As new azo dyestuff intermediates and related azo dyestuffs, the compositions of matter represented by the following probable formula wherein X represents S0 or S, R and R represent benzene or naphthalene residues in which the COOH and the X are ortho to the OH group, R represents SO H, COOH, CHO, CN or H, R represents CH COOH or COOC H and Z represents the structure wherein R represents a coupled residue of an azo dye component from a diazo compound of the benzene or naphthalene series.

15. As new dyestufl intermediates, compounds having the probable formula wherein R represents a pyra-zolone ring, B

, and R represent benzene or naphthalene residues, X represents S0 or S, and in which the X and the CQOH group are attached to R, in the ortho positions in respect to the OH group, the said intermediates being light colored powders easily soluble in alkalies, very sparingly soluble in water and dilute mineral acids, and readily coupled with diazotized coupling components of the benzene or naphthalene series to form brown to yellow dyestufis. w

16. As new dyestuff intermediates, compounds having the probable formula wherein R represents a benzene or naphthalene residue, R represents a benzene residue, X represents S0 or S, R represents SO H, CHO, CN or H, and R represents CH COOH or COOCJ-l and in which the X and the COOH, group are attached to R in the ortho positions in respect to the OH group.

17. As new dyestuif intermediates, compounds having the probable formula wherein R represents a benzene residue, R

represents I-LCl-l or Cl, R represents sO H,

CGGH, CHO, CN or H, R represents CH $2015 or CO'OC H and X represents S or 18. As new dyestuff intermediates, compounds having the probable formula wherein R represents a benzene or naphthalene residue, R represents a benzene residue,

represents SO H, CHO, CN or H, and R represents CH COOH or COOC H and in which the S0 and the COOH group are at tached to R in the ortho positions in respect to the OH group;

20. As new dyestuff intermediates, compounds havin the probable formula no 0 0 on l I Ills Q WK O=O N R4 HzC C-Ru wherein R represents a benzene residue, R represents H, CH or C1, R represents SO H, CGOH, CHO, UN or H, and R represents CH COOH or COOC H 21. As a new dyestuif intermediate, the compound having the probable formula GOOH SOaH 22.1 120 dyes carrying a chelate group and adapted for mordant dyeing with the chelate group separated from the chromophore group by a sulphone or sulphide bridge, said azo dyes being pyrazolone derivatives having the probable formula wherein X represents SO or S, R and R represent benzene or naphthalene residues, R represents a pyrazolone ring and R repre sents a coupled residue of an azo dye component derived from a diazo compound of the benzene or naphthalene series and in which the X and the COOH groups are attached to the R in the ortho positions to the OH group, the said dyestuffs producing shades which are substantially unchanged when chromed.

E23. Azo dyes carrying a chelate group and adapted for mordant dyeing, with the chelate group separated from the chromophore group by a sulphone or sulphide bridge, said azo dyes being pyrazolone derivatives having the probable formula HOOC no wherein X represents $0 or S, R and R represent benzene or naphthalene residues, R represents a pyrazolone ring and R,- represents a coupled residue from a diazotized monoamino coupling component of the benzene or naphthalene series and in which the X and the COOH groups are attached to R in the ortho positions to the OH groups. 24. Azo dyes carrying a chelate group and adapted for mordant dyeing, with the chelate group separated from the chromophore group by a. sulphur containing bridge, said a zo dyes being pyrazolone derivatives having the probable formula wherein X represents S0 or S, R represents a benzene residue, R, represents H, CH or Cl, represents SO H, COOH, CHO, CN or H, R represents CH COOH or COOC H and R- represents a coupled residue of an azo dye component derived from a diazo compound of the benzene or naphthalene series.

25. Azo dyes carrying a chelate group and adapted for mordant dyeing, with the chelate group separated from the chromophore group by a sulphone bridge, said azo dyes being pyrazolone derivatives havingthe probable formula wherein R and R represent benzene or naphthalene residues, R represents a pyrazolone wherein R represents a benzene residue, 'R represents H, CH or Cl, R represents SOJ'I, COOH, CHO, CN or H and R represents CH COOH or COOC H and R represents a coupled residue from a diazotized coupling component of the benzene or naphthalene series, the said dyestuffs producing shades which are substantially unchanged when chromed.

27. As a new dyestuff, a compound having the probable formula COOH -so3n on soz 28. As a new dyestuff, a compoundhaving the probable formula COOH noo

In testimony whereof I aflix my signature.

MORDECAI MEN DOZA.

Certificate of Correction Patent No. 1,841,623. Granted January 19, 1932, to MORDE CAI MENDOZA.

It is hereby certified that error appears in the printed specification of the abovenumbered patent requiring correction as follows: Page 2, after line 23 strike out the formula and insert instead a page 4, line 100, strike out the word pyrazolone page 6, line 71, claim 10, after and insert the X and; and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Ofiice.

Signed and sealed this 1st day of March, A. D. 1982.

[SEAL] M. J. MOORE,

Acting G-ommissioner of Patents. 

